Two-Dimensional Square-Grid versus One-Dimensional Double

Jul 7, 2005 - Ki-Min Park,† Il Yoon,† Joobeom Seo,† Ji-Eun Lee,† Jineun Kim,† Kyu Seong Choi,‡. Ok-Sang Jung,§ and Shim Sung Lee*,† ...
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CRYSTAL GROWTH & DESIGN

Two-Dimensional Square-Grid versus One-Dimensional Double-Stranded Networks: Counterion Regulation of the Formation of Macrocycle-Based Copper(I) Coordination Frameworks

2005 VOL. 5, NO. 5 1707-1709

Ki-Min Park,† Il Yoon,† Joobeom Seo,† Ji-Eun Lee,† Jineun Kim,† Kyu Seong Choi,‡ Ok-Sang Jung,§ and Shim Sung Lee*,† Department of Chemistry and Institute of Natural Sciences, Gyeongsang National University, Chinju 660-701, South Korea, Department of Chemistry, Kyungnam University, Masan 631-701, South Korea, and Department of Chemistry, Pusan National University, Pusan 609-735, South Korea Received May 19, 2005;

Revised Manuscript Received June 20, 2005

ABSTRACT: A two-dimensional square-grid-shaped coordination polymer incorporating the dithiaoxa macrocycle (1), [Cu(1)CN]n (2), has been prepared by a self-assembly process involving the interaction of 1 with CuCN; the parallel reaction of 1 with CuI afforded the one-dimensional double-stranded coordination polymer [Cu(1)I]n (3). Combined with a suitable metal ion, both cyclic and acyclic multidentate ligands have been frequently employed for the synthesis of organic-inorganic composite arrays.1 It is now clear from such crystal engineering studies that to generate a desired network, attention needs to be focused on the use of a rationally designed ligand system as well as on the coordination characteristics of the chosen metal ion. A more subtle effect affecting the final topological arrangement may arise from anion control or regulation.2 The use of thia-containing macrocycles as building blocks in such systems yields the potential of binding soft metals in either the ligand’s endo- or exo-cyclic modes; in particular, exo-coordination has now been well documented for such sulfur-containing ligand systems.3 On the basis of prior studies, the use of copper(I) (favoring tetrahedral coordination) in the presence of halide4 or cyanide5 ions gives the possibility of promoting the formation of a framework because of the strong coordinating nature of these ions and their ability to act as connectors between different copper centers. Thus, the cyanide ion is capable of functioning as a straight connector to yield a linear CuCN-Cu unit.5 Examples of copper(I) iodide systems incorporating thia ligands in which iodide bridges two or more copper centers are known. Typically, these are neutral coordination polymers, and when the iodide is present as an L-type connector the Cu-I-Cu bond angles have been shown to lie in the range 55-84°.4 In view of the above discussion, we have investigated the effect of anion variation on the assembly of new coordination polymers formed from the thia-oxa macrocycle 16,7 and copper(I) cyanide or iodide (Scheme 1). Two unique structures have been generated: the two-dimensional (2D) grid-type system (2) and the one-dimensional (1D) polymeric array (3). Both of these serve to illustrate the profound change in structure that can arise from a simple change in the counterion available to the system. Complex 28 was prepared by the reaction of an equimolar amount of 1 and CuCN in MeOH/acetonitrile (1:1) under reflux conditions for 5 h. The reaction mixture was filtered, and slow evaporation of the filtrate produced colorless crystals suitable for X-ray analysis (yield; ca. 30%). * Corresponding author. E-mail: [email protected]. Tel.: +82-55-7516021. Fax.: +82-55-753-7614. † Gyeongsang National University. ‡ Kyungnam University. § Pusan National University.

Scheme 1

It is clear from the X-ray structure9 that 2, [Cu(1)CN]n, crystallizes to yield an interesting square-grid-type framework consisting of linear polymeric CuCN chains thialinked by bridging macrocyclic units 1 (Figure 1a). The asymmetric unit contains one copper atom, one cyanide ion, and one macrocycle (Figure 1b). A distortion from tetrahedral at the copper(I) is apparent with the C21-Cu-N22i angle being 130.3(2)°, while the smallest angle, S1-Cu-S2ii, is 95.20(5)°. The Cu-S bond distances [Cu-S1 2.4171(14), Cu-S2ii 2.4678(15)] are about 0.1 Å longer than those found in other fourcoordinate copper(I) systems (≈2.35 Å).10,11 The 2D sheets of 2, which are considerably puckered due to the distorted tetrahedral geometry of the copper atoms, have a mean plane parallel to (200). The dimensions of each rectangular unit, incorporating Cu atoms at each corner, were observed to be approximately 4.9 and 10.3 Å. A network complex with a similar connectivity involving linked CuCN and linear organodiimines has been reported by Zubieta et al.5e To our knowledge, however, 2 is the first example in which an exo-dentate thia-oxa macrocycle, a thiaphilic metal ion, and a coordinating anion have been employed simultaneously for the construction of a squaregrid-type coordination polymer. Colorless single crystals of 3,8 {[Cu(1)I](CH3CN)}n, were obtained on slow evaporation of an equimolar mixture of

10.1021/cg050220u CCC: $30.25 © 2005 American Chemical Society Published on Web 07/07/2005

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Crystal Growth & Design, Vol. 5, No. 5, 2005

Communications complexes.10,11 Four other examples of thia macrocycles yielding coordination polymers incorporating doublestranded 1D copper(I) halides are known.11 In conclusion, the combination of framework-building components [Cu(I) and 1] and a framework-regulator (CNor I-) has resulted in the formation of two new extended frameworks corresponding to the square-grid coordination polymer (2) and the double-stranded coordination polymer (3), respectively. These results serve well to illustrate how anion control may promote the assembly of very different types of coordination arrays. Acknowledgment. This work was supported by Korea Science and Engineering Foundation (R01-2004-000-103210). We thank Professor L. F. Lindoy, University of Sydney, for assistance. Supporting Information Available: Crystallographic data for 2 and 3 in CIF format; table of crystal and experimental data for 2 and 3; figures of asymmetric units of 3 and 2D square-grid structure (top view) of 2. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data for the structure reported in this paper also available at the Cambridge Crystallographic Data Centre, with the CCDC reference number 186944 (for 2) and 186943 (for 3).

References

Figure 1. (a) 2D square-grid structure and (b) asymmetric unit of 2, [Cu(1)CN]n.

Figure 2. Double-stranded 1D structure of 3, {[Cu(1)I](CH3CN)}n. The solvent molecules have been omitted for clarity.

copper(I) iodide and 1 in acetonitrile. X-ray analysis9 revealed that this product has a double-stranded polymeric chain structure (Figure 2). The framework contains two exo-bidentate macrocycles bridging a dinuclear iodobridged copper unit, Cu-I2-Cu, showing a rhomboid geometry. An alternating arrangement of a pair of macrocycles and a square-dimeric Cu-I2-Cu unit forms a large cyclic dimer, corresponding to a 22-membered ring. The Cu coordination sphere has a distorted tetrahedral shape, with the “tetrahedral” angles falling in the range 100.29(8)123.94(8)°. The bond distances to sulfur [Cu-S1 2.333(3) Å, Cu-S2ii 2.302(2) Å] are reasonably similar and compare well to those found in other copper(I)-thia macrocyclic

(1) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460. (b) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31, 474. (c) Blake, A. J.; Champness, N. R.; Hubberstey, P.; Schro¨der, M.; Withersby, M. Coord. Chem. Rev. 1999, 183, 117. (d) Albrecht, M. Chem. Rev. 2001, 101, 3457. (2) (a) Blake, A. J.; Champness, N. R.; Khlobystov, A. N.; Lemenovskii, D. A.; Li, W.-S.; Schro¨der, M. Chem. Commun. 1997, 1139. (b) Carlucci, L.; Ciani, G.; Proserpio, D. M.; Sironi, A. Inorg. Chem. 1998, 37, 5941. (c) Jung, O.-S.; Kim, Y.; Lee, Y.-A.; Park, J. K.; Chae, H. K. J. Am. Chem. Soc. 2000, 122, 9921. (d) Kang, Y.; Lee, S. S.; Park, K.-M.; Lee, S. H.; Kang, S. O.; Ko, J. Inorg. Chem. 2001, 40, 7027. (e) Noro, S.; Kitaura, R.; Kondo, M.; Kitagawa, S.; Ishii, T.; Matsuzaka, H.; Yamashita, M. J. Am. Chem. Soc. 2002, 124, 2568. (3) (a) Wolf, R. E., Jr.; Hartman, J. R.; Storey, J. M. E.; Foxman, B. M.; Cooper, S. R. J. Am. Chem. Soc. 1987, 109, 4328. (b) Robinson, G. H.; Sangokova, S. A. J. Am. Chem. Soc. 1988, 110, 1494. (c) Buter, J.; Kellog, R. M.; van Bolhuis, F. J. Chem. Soc., Chem. Commun. 1991, 910. (d) Hill, S. E.; Feller, D. J. Phys. Chem. A 2000, 104, 652. (e) Jin, Y.; Yoon, I.; Seo, J.; Lee, J.-E.; Moon, S.-T.; Kim, J.; Han, S. W.; Park, K.-M.; Lindoy, L. F.; Lee, S. S. Dalton Trans. 2005, 788. (4) (a) Graham, P. M.; Pike, R. D.; Sabat, M.; Bailey, R. D.; Pennington, W. T. Inorg. Chem. 2000, 39, 5121. (b) Victoriano, L. I.; Garland, M. T.; Vega, A. Inorg. Chem. 1997, 36, 688. (c) Hou, H.; Long, D.; Xin, X.; Huang, X.; Kang, B.; Ge, P.; Ji, W.; Shi, S. Inorg. Chem. 1996, 35, 5363. (d) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Nakagawa, S. J. Chem. Soc., Dalton Trans. 1996, 1525. (5) (a) Stocker, F. B.; Troester, M. A.; Britton, D. Inorg. Chem. 1996, 35, 3145. (b) Chesnut, D. J.; Kusnetzow, A.; Birge, R.; Zubieta, J. Inorg. Chem. 1999, 38, 5484. (c) Stocker, F. B.; Staeva, T. P.; Rienstra, C. M.; Britton, D. Inorg. Chem. 1999, 38, 984. (d) Chesnut, D. J.; Kusnetzow, A.; Birge, R.; Zubieta, J. J. Chem. Soc., Dalton Trans. 2001, 2581. (e) Chesnut, D. J.; Plewak, D.; Zubieta, J. J. Chem. Soc., Dalton Trans. 2001, 2567. (6) Lee, Y. H.; Lee, S. S. J. Inclusion Phenom. Macrocyclic Chem. 2001, 39, 235. (7) Macrocycle 1 was synthesized using a similar procedure to that described in our previous study.6 (8) Selected data for 2: mp 116-119 °C, IR (KBr)/cm-1: 2922, 2854, 2112(CN-), 1598, 1493, 1449, 1243, 1117, 950, 754. 1H NMR (500 MHz, DMSO-d ): δ 7.30-6.93 (m, 8H, Ar), 6 4.34 (s, 4H, OCH2CH2O), 3.92 (s, 4H, SCH2Ar), 3.46 (t, 4H, OCH2CH2S, J 6.0 Hz), 2.59 (t, 4H, OCH2CH2S, J 6.0 Hz).

Communications 13C

NMR (125 MHz, DMSO-d6): δ 157.0, 131.0, 129.1, 127.8, 121.6, 112.7, 71.2, 67.7, 31.8, 30.8. m/z (ESI) 439 [Cu(1)CN-CN]+. Anal. Calc. for C20H24O2S2CuCN‚CH3CN: C, 54.47; H, 5.37. Found: C, 54.46; H, 5.77%. For 3: mp 9193 °C, IR (KBr)/cm-1: 2930, 2867, 1599, 1492, 1448, 1241, 1111, 954, 753. 1H NMR (500 MHz, DMSO-d6): δ 7.346.92 (m, 8H, Ar), 4.37 (s, 4H, OCH2CH2O), 3.89 (s, 4H, SCH2Ar), 3.48 (t, 4H, OCH2CH2S, J 6.0 Hz), 2.62 (t, 4H, OCH2CH2S, J 6.0 Hz). 13C NMR (125 MHz, DMSO-d6): δ 155.1, 129.0, 127.0, 125.8, 119.5, 110.7, 69.1, 65.8, 29.9, 28.9. m/z (ESI) 439 [Cu(1)I-I]+. Anal. Calc. for C40H48O4S4Cu2I2‚CH3CN: C, 42.93; H, 4.37. Found: C, 43.01; H, 4.41%. (9) Crystal data for 2: colorless, 0.25 × 0.20 × 0.20 mm, C21H24CuNO3S2, Mr ) 466.07, monoclinic, space group P21/c, a ) 12.8498(14), b ) 9.0701(10), c ) 19.779(2) Å, β ) 100.132(2)°, V ) 2269.3(4) Å3, Z ) 4, Dc ) 1.364 g cm-3, T ) 298(2) K, µ ) 1.166 mm-1, F(000) ) 968, 14 314 reflections measured (5500 unique), R [I > 2σ(I)] ) 0.0658, wR2 (all data) ) 0.2035, GOF ) 0.953 for 253 parameters. For 3: colorless, 0.20 × 0.20 × 0.10 mm, C22H27CuINO3S2, Mr ) 608.01, triclinic, space group P1 h , a ) 9.9125(19), b )

Crystal Growth & Design, Vol. 5, No. 5, 2005 1709 10.2339(19), c ) 13.055(2) Å, R ) 102.880(4), β ) 102.706(4), γ ) 94.705(3)°, V ) 1247.4(4) Å3, Z ) 2, Dc ) 1.619 g cm-3, T ) 298(2) K, µ ) 2.302 mm-1, F(000) ) 608, 8210 reflections measured (5759 unique), R [I > 2σ(I)] ) 0.0759, wR2 (all data) ) 0.2600, GOF ) 0.988 for 271 parameters. The structure was solved by direct methods and refined by full matrix least squares against F2 for all data using SHELXTL software.12 (10) Brooks, N. R.; Brake, A. J.; Chapmpness, N. R.; Cooke, P. A.; Hubberstey, P.; Proserpio, D. M.; Wilson, C.; Schro¨der, M. J. Chem. Soc., Dalton Trans. 2001, 456. (11) (a) Chen, L.; Thompson, L. K.; Bridson, J. N. Can. J. Chem. 1992, 70, 2709. (b) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T.; Maekawa, M.; Suenaga, Y.; Nakagawa, S. J. Chem. Soc., Dalton Trans. 1996, 1525. (c) Adams, R. D.; Huang, M.; Johnson, S. Polyhedron 1998, 17, 2775. (d) Heller, M.; Sheldrick, W. S. Z. Anorg. Allg. Chem. 2003, 629, 1589. (12) Bruker, SHELXTL-PC, Version 5.10; Bruker-Analytical X-ray Services: Madison, WI, 1998.

CG050220U